CNT Buckypaper Roll-to-Roll Deposition for Thick Films

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Solution Overview

Problem

Existing methods for producing carbon nanotube (CNT) buckypapers face challenges in scaling up to produce thick, meter-long films efficiently, due to issues with solubility, processing difficulties, and the need for surfactants or binders.

Innovation Solution

A roll-to-roll compatible deposition technique is used to produce large area, meter-long thick films of CNT buckypaper by preparing a dissolved CNT salt solution, depositing it onto a porous filter, and then drying and delaminating the buckypaper to form a freestanding film without the need for surfactants or binders.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If traditional filtration method is used to produce CNT buckypaper, then the buckypaper can be obtained, but the production process is extremely challenging and time-consuming when scaling up to produce thick, meter-long films

Engineering Contradiction:
Improveproduction efficiency of thick meter-long filmsVSAvoiddifficulty of scaling up production
Core Design Contradiction:
ProductivityVSEase of manufacture

Solution Approach 1:

The patent changes the physical and chemical parameters of the CNT material by functionalizing the CNT surfaces and forming CNT salts, which fundamentally alters the solubility and processability characteristics. This enables the material to be processed in solution form through roll-to-roll deposition, achieving meter-long thick films with high productivity that were previously impossible with traditional filtration methods

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces the mechanical filtration process with a chemical solution-based deposition process. Instead of filtering CNT suspensions through membranes (mechanical separation), the invention uses roll-to-roll deposition of CNT salt solutions followed by controlled oxidation to form the final buckypaper, dramatically simplifying the manufacturing process and enabling continuous production of long films

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

2Quantity of substance

If CNTs are processed in film form using traditional methods, then films can be produced, but the poor solubility of CNTs results in low concentrated dispersions requiring large volumes of solution

Engineering Contradiction:
ImproveCNT concentration in dispersionVSAvoidsolution volume required
Core Design Contradiction:
Quantity of substanceVSLoss of substance

Solution Approach 1:

The patent fundamentally changes the solubility parameter of CNTs by converting them into soluble salt forms through chemical functionalization. The CNT salts can be dissolved in polar aprotic solvents to achieve high concentrations (up to 5 mg/mL), eliminating the need for large volumes of dilute suspensions required by traditional methods

Inventive Principle:
Principle #35Parameter changes

3Volume of moving object

If thick films of CNT buckypaper are deposited using spray-coating, then film thickness can be increased, but the low CNT content in solution makes the deposition process very slow

Engineering Contradiction:
Improvefilm thicknessVSAvoiddeposition speed
Core Design Contradiction:
Volume of moving objectVSProductivity

Solution Approach 1:

The patent changes the concentration parameter of the CNT solution by using soluble CNT salt formulations that can achieve high CNT concentrations (up to 5 mg/mL). This allows thick films to be deposited rapidly through roll-to-roll methods, achieving both the desired film thickness and high deposition speed, unlike spray-coating which is limited by low CNT content in traditional suspensions

Inventive Principle:
Principle #35Parameter changes

4Ease of manufacture

If surfactants or binders are added to process CNTs, then the processing difficulty is reduced, but the purity and performance of the final buckypaper deteriorates

Engineering Contradiction:
Improveprocessability of CNTsVSAvoidperformance and purity of buckypaper
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent uses CNT salts as an intermediary form that enables processing without requiring traditional surfactants or binders. The salt formulation acts as a temporary processing aid that can be completely removed through oxidation and washing steps, leaving pure CNT buckypaper with superior performance. This intermediary approach solves the contradiction by enabling easy processing while maintaining final product purity

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent employs a process where the CNT salt formulation and associated processing chemicals are completely discarded through oxidation and washing steps. The temporary salts and surfactants used during processing are removed to recover pure CNT buckypaper, ensuring high purity and performance in the final product while still benefiting from the ease of processing provided by the salt formulation during manufacturing

Inventive Principle:
Principle #34Discarding and recovering

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This method allows for the production of thick, stable CNT films with low sheet resistance, high electrical conductivity, and excellent mechanical stability, enabling their use in thermoelectric modules and battery electrodes with improved performance and longevity.

Implementation Method 1

preparing a dissolved CNT salt using a procedure comprising the following step: i) providing a stock solution of reductive alkali metal, preferably the alkali metal is selected from potassium or sodium, naphthalenide (Np) in a polar aprotic solvent

Methodology Applied
Scientific EffectReduction: Reduction

Implementation Method 2

depositing the solution obtained in a) via roll-to-roll compatible deposition method onto a porous filter used as temporary substrate, preferably the temporary substrates are porous PTFE filter sheets, in presence of an oxidizing atmosphere at a pressure of between 0,8 and 1,5 bar

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 3

removing the solvent and partially drying the wet buckypaper obtained in b) by applying a rough vacuum across the porous filter substrate

Methodology Applied
Scientific EffectEvaporation: Evaporation

Data Source

PatentEP4570751A1Method for obtaining microns thick, meter long cnts buckypaper and its uses in thermoelectrics and as current collector of a battery
Publication Date: 2025.06.18 CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS (CSIC)
  • EP4570751A1 patent drawingFigure 1(a)~1(c)
  • EP4570751A1 patent drawingFigure 2
  • EP4570751A1 patent drawingFigure 3

AI summary

The invention relates to a new method for preparing more than micron thick and meter-long carbon nanotube (CNT) buckypapers and more particularly using a roll-to-roll compatible fabrication approach. In addition, the buckypaper is obtained for the fabrication of the n- and p-type components of the thermoelectric module, as well as for electrode components in chemical storage devices through a post-deposition process involving partial oxidation of the CNTs and neutralization of the dopant.